JP3290763B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having a low coefficient of linear expansion, excellent dimensional stability, and an excellent balance between impact resistance and rigidity.

[0002]

2. Description of the Related Art In recent years, automobile parts have rapidly become plastic in order to improve fuel efficiency by reducing the weight of automobiles, and interior parts such as instrument panels, console boxes, glove boxes, handles, trims, moldings, Various plastic materials have been used not only for exterior parts such as lamp housings, front grilles, mudguards, and side bumpers, but also for parts such as bumpers, fascias, fenders, door panels, and bodies that were conventionally made of metal.

Examples of plastics used for such automobile parts include inorganic reinforced plastics such as RIM urethane, composite polypropylene, and G / F reinforced polyamide, and polymer alloy materials such as PC / PBT and PPE / PA. Can be Among these materials, composite polypropylene is, for example, a polypropylene-based composition obtained by blending an ethylene-propylene copolymer rubber partially crosslinked with polypropylene, oil and the like, as disclosed in JP-A-53-1.
No. 45857, No. 54-16554 and No. 57-13
No. 5847, and PPE / PA
For example, a composition obtained by adding a rubber modified with a polar group-containing compound as an impact resistance improving material to a combination of polyphenylene ether and polyamide is disclosed in JP-A-56-497.
No. 53, and in order to further improve the balance between low-temperature impact resistance and rigidity, a composition comprising a modified polyphenylene ether intermediate, a polyamide and an impact resistance improving material is disclosed in JP-A-1-19664. Proposed.

[0004] In particular, the materials used for fascias, fenders and door panels have come to require even higher levels of performance than conventional plastic parts. For example, impact resistance; the property of absorbing the energy at the time of collision by deforming and then recovering,
Characteristics of ductile impact fracture at low temperatures. Dimensional stability due to low-temperature expansion coefficient: When a plastic molded product after application is used in a high-temperature environment, the degree of thermal expansion between the paint and the base plastic is different. In many cases, appearance and design are deteriorated. In addition, large molded plastic products are
For example, when used in combination with a molded article such as wood or metal, the degree of thermal expansion is different in a high-temperature use environment, and thus, at present, problems such as dimensional differences and poor meshing have occurred. Therefore, it is desired to establish a material technology that satisfies the above conditions, that is, an improvement in impact resistance of plastic and an improvement in dimensional stability at high temperatures (a technology for controlling a thermal expansion coefficient).

[0005]

In conventional automotive plastic materials, dimensional accuracy (linear expansion coefficient) at high temperatures is high.
It was difficult to achieve both high impact strength at a high level. As a general countermeasure against this, it is well known that the impact resistance is improved by, for example, blending a high content of an elastomer, but the dimensional accuracy (linear expansion coefficient) at high temperatures is deteriorated. Therefore, as a method to improve the impact resistance by making the elastomer a certain amount,
There is generally a morphology improvement. This is a method of increasing the compatibilizing ability between different kinds of thermoplastic resins by using a special blending technique or a blending technique, and making the domain particle size in a micro-dispersed form (domain-matrix structure) fine. Dimensional accuracy at high temperature (linear expansion coefficient)
Is not improved.

In order to improve the dimensional accuracy (linear expansion coefficient), a method of blending an inorganic filler can be considered, but in this case, the molded product tends to be brittle, and the impact resistance level is lowered. Shows that the impact fracture mode is responsible for the brittleness, and its use is significantly limited.

Accordingly, an object of the present invention is to provide a resin composition which improves the above-mentioned drawbacks, has excellent dimensional accuracy (linear expansion coefficient) at high temperatures, and has an excellent balance between low-temperature impact resistance and rigidity.

[0008]

In order to solve this problem, the present inventors have studied the relationship between the dispersion state of thermoplastic resins mixed inhomogeneously with one another and the dimensional stability, especially the coefficient of linear expansion and impact resistance. As a result of intensive studies, among the thermoplastic resins mixed inhomogeneously with each other, the other two thermoplastic resins are dispersed in the form of particles in one thermoplastic resin. (Sea-island structure) Alternatively, one thermoplastic resin is dispersed in one thermoplastic resin in the form of particles, and the remaining thermoplastic resin is present in the thermoplastic resin dispersed in the form of particles ( Rather than a sea-island-lake structure), one thermoplastic resin forms a form that is dispersed in a network, in other words, a network, and the thermoplastic resin is present at the interface between the other two thermoplastic resins. In addition, they have found that when the inorganic filler component is substantially present in the crystalline resin component, it has high dimensional stability and impact resistance which were not expected in conventional products, and thus completed the present invention.

That is, the present invention relates to a crystalline thermoplastic resin component (a), an amorphous thermoplastic resin component (b) which is heterogeneously mixed with the component (a), a component (a) and a component (b). In the resin composition comprising the thermoplastic resin component (c) and the inorganic filler (d) to be uniformly mixed, the component (c) forms a network form, and the component (c) substantially comprises the component (a) and the component ( A thermoplastic resin composition which is present at the interface of b) and wherein the component (d) is substantially present in the component (a).

[0010] In particular, the components (a) and / or closed by the network of the components (c) existing in a square having a side of 1 µm.
Alternatively, the thermoplastic resin composition has a form in which the number m of regions of the component (b) makes the average value of the index R represented by the formula (I) 0.9 or less.

[0011]

(Equation 2)

Here, a method of confirming a dispersion form of one thermoplastic resin in one thermoplastic resin composition and a method of calculating m, which are main items of the present invention, will be described.

First, for example, a part is cut out from, for example, a molded product or a pellet obtained by kneading, dyed with RuO ₄ and OsO ₄ , and then an ultra-thin section is cut using an ultramicrotome (Ultracut N manufactured by Reichert). It is prepared and observed with a transmission electron microscope (JEM100CX manufactured by JEOL Ltd.). The thermoplastic resin of the component (c) is observed to be black by dyeing, and its existing state can be easily observed. Furthermore, the dispersed state of the thermoplastic resin of the component (c) is binarized by an image processing / analyzing apparatus (Spica 2 manufactured by Nippon Avionics Co., Ltd.), and the photograph is present in a square of 1 μm on a side.
The number m of regions of the other component resin closed by the network of the thermoplastic resin (c) is calculated, and R is calculated by the formula (I).
Is calculated. Perform this analysis on 10 or more, preferably 30 or more typical locations of the molded article or pellet,
The average value is obtained and used as an index of the network structure.

Hereinafter, the present invention will be described in detail.

<Crystalline Thermoplastic Resin (a)> The crystalline thermoplastic resin (a) has a non-glass-like property having a clear crystal structure or a crystallizable molecular structure.
It has a measurable heat of fusion and a distinct melting point.
Melting points and heats of fusion are measured using a differential scanning calorimeter (eg, PERK
It can be measured using DSC-II manufactured by IN-ELMER. That is, using this apparatus, the heat of fusion heats the sample to a temperature above the expected melting point at a rate of 10 ° C. per minute and then cools to 20 ° C. at a rate of 10 ° C. per minute. After leaving it for about 1 minute, it is heated again at a rate of 10 ° C. per minute and measured again, and the value of the heat of fusion measured in the cycle of temperature increase and decrease becomes a constant value within the experimental error range. Adopt something. The thermoplastic resin (a) used in the present invention has a heat of fusion of 1 calorie /
Defined as grams or more.

A specific example will be described below.

(A-1) Saturated Polyester As an example of the crystalline thermoplastic resin (a) used in the present invention, a saturated polyester is mentioned, and various polyesters can be used.

For example, as one of them, a dicarboxylic acid or a lower alkyl ester, an acid halide or an acid anhydride derivative thereof, a glycol or
And a thermoplastic polyester produced by condensing with a phenol.

Specific examples of aromatic or aliphatic dicarboxylic acids suitable for producing the polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid. acid,
Isophthalic acid, p, p'-dicarboxydiphenylsulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,6-naphthalene dicarboxylic acid or 2,7 -Naphthalene dicarboxylic acid and the like or a mixture of these carboxylic acids.

Examples of the aliphatic glycol suitable for producing a saturated polyester include linear alkylene glycols having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6.
-Hexanediol, 1,12-dodecanediol and the like are exemplified. Examples of the aromatic glycol include p-xylylene glycol, and examples of the dihydric phenol include pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds.
Other suitable glycols also include 1,4-cyclohexanedimethanol.

Another preferred saturated polyester is a polyester obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone) and the like.

Further, as another preferred saturated polyester, a polymer capable of forming a liquid crystal in a molten state (Thermotr)
There is polyester as opic Liquid Crystal Polymer (TLCP). Typical polyesters that fall into these categories are Eastman Kodak X7G, Dartco Xydar, Sumitomo Chemical Econol, and Celanese Vectra.

Among the above-mentioned saturated polyesters,
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly (1,4-cyclohexane dimethylene terephthalate) (PCT), liquid crystalline polyester and the like are suitable for the thermoplastic resin composition of the present invention. Is a highly saturated polyester.

The saturated polyester used here is 60/60 of phenol / 1,1,2,2-tetrachloroethane.
Intrinsic viscosity measured at 20 ° C. in a 40% by weight mixed solution is 0.
A range of 5 to 5.0 dl / g is preferred. More preferably,
1.0 to 4.0 dl / g, particularly preferably 2.0 to 3.0 dl / g.
It is 5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the impact resistance is insufficient, and when the intrinsic viscosity is 5.0 dl / g or more, the moldability is poor.

(A-2) Polyamide Polyamide is mentioned as an example of the crystalline thermoplastic resin (a). The polyamide used in the present invention has a -CO-NH- bond in the polymer main chain and can be melted by heating. Things. Typical examples are nylon 4, nylon 6, nylon 6,6, nylon 4,6, and nylon 1.
2, nylon 6,10 and the like. In addition, known low-crystalline and amorphous polyamides containing monomer components such as aromatic diamines and aromatic dicarboxylic acids can also be used.

The preferred polyamide is nylon 6 or nylon 6,6, with nylon 6 being particularly preferred.

The polyamide used in the present invention preferably has a relative viscosity of 2.0 to 8.0 (measured in 98% concentrated sulfuric acid at 25 ° C.).

(A-3) Polyolefin Polyolefin is mentioned as an example of the crystalline thermoplastic resin, and the polyolefin used in the present invention is ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene- 1,4-methylpentene-
1, homopolymers of α-olefins such as heptene-1 and octene-1, random or block copolymers of these α-olefins, and the majority of these α-olefins with other unsaturated monomers Copolymers such as random, graft or block, oxidation to these olefin polymers,
It has been subjected to treatment such as halogenation and sulfonation,
It exhibits crystallinity derived at least partially from polyolefin, and preferably has a crystallinity of 20% or more. These may be used alone or in combination of two or more.

Examples of other unsaturated monomers include: acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride, arylmaleimide, Unsaturated carboxylic acids such as alkyl maleic imides or derivatives thereof; vinyl esters such as vinyl acetate and vinyl butyrate; aromatic vinyl compounds such as styrene and methyl styrene; vinyl trimethylmethoxysilane and γ-methacryloyloxypropyl trimethoxysilane Vinyl silane; non-conjugated dienes such as dicyclopentadiene and 4-ethylidene-2-norbornene.

The polyolefin is obtained by polymerization or modification by a known method, but may be appropriately selected from commercially available ones.

Among them, propylene, butene
Homopolymers of 1,3-methylbutene-1 and 4-methylpentene-1 or copolymers containing a majority of these are preferred, and especially crystalline propylene-based polymers, that is, crystalline propylene homopolymer and crystalline propylene -Α-olefin block or random copolymer, a copolymer of these crystalline propylene polymers and α-olefin rubber, that is, a copolymer of a plurality of rubber-like α-olefins, or a mixture of a plurality of α-olefins and a non-conjugated diene. Mixtures are preferred in terms of balance of mechanical properties.

The melt flow rate (MFR) (230 ° C., load 2.16 kg) of these crystalline propylene polymers or a mixture containing these and an α-olefin rubber is preferably in the range of 0.01 to 250 g / 10 minutes. Preferably, 0.0
The range is more preferably from 5 to 150 g / 10 minutes, particularly preferably from 0.1 to 50 g / 10 minutes. When the value of MFR is lower than this range, there is a problem in molding processability, and when the value is higher than this range, the level of balance of mechanical properties is low, which is not preferable.

Some of these include higher molecular weight ones.
Also included are those in which the molecular weight is changed by heat treatment in the presence of a radical generator, for example, an organic peroxide or the like, to fall within the MFR range.

Examples of the crystalline thermoplastic resin (a) other than the above include polyacetal (POM), fluororesin, polyetheretherketone, etc., preferably saturated polyester, polyamide and polyolefin, more preferably Are saturated polyesters and polyamides.

The crystalline thermoplastic resin (a) used in the present invention may be used in combination of two or more kinds.

<Amorphous thermoplastic resin (b)> The amorphous thermoplastic resin (b) generally has glass-like properties and exhibits a glass transition temperature when heated. In this case, it is preferable to use an amorphous thermoplastic resin having a glass transition temperature of 50 ° C. or higher. Amorphous thermoplastic resins do not show a clear melting point or a measurable heat of fusion, but in the present invention, include those which show some crystallinity when cooled slowly, and the effects of the present invention. Is included within a range that does not significantly impair the above. The glass transition temperature, melting point, and heat of fusion can be measured using a differential scanning calorimeter. Examples of this include the apparatus and measuring method described in the section of <Thermoplastic resin (a)>. Amorphous thermoplastics in the present invention are defined as those having a heat of fusion of less than 1 cal / gram as measured by this method.

A specific example will be described below.

(B-1) Polyphenylene ether Examples of the amorphous thermoplastic resin (b) used in the present invention include polyphenylene ether, which is represented by the general formula (II)

[0039]

Embedded image

Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group; ² represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and n represents an integer of 10 or more.

A homopolymer or a copolymer having a structure represented by the following formula: Suitable examples of primary alkyl groups for Q ¹ and Q ² are methyl, ethyl, n-propyl, n-butyl,
n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4
-Methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-
It is ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, particularly an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable homopolymers of polyphenylene ether include, for example, those comprising 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include the above units and 2,3,6-trimethyl-1,
It is a random copolymer comprising a combination with a 4-phenylene ether unit. Many suitable homopolymers or random copolymers are described in patents and literature. For example, polyphenylene ethers containing molecular constituents that improve properties such as molecular weight, melt viscosity and / or impact strength are also suitable.

The polyphenylene ether used here has an intrinsic viscosity of 0.3 in 30 ° C. measured in chloroform.
It is preferably from 2 to 0.8 dl / g. More preferably, the intrinsic viscosity is 0.2 to 0.5 dl / g, and particularly preferably, the intrinsic viscosity is 0.25 to 0.4 dl / g.

If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance of the composition is insufficient, and if it exceeds 0.8 dl / g, the moldability of the composition and the appearance of the molded article are difficult.

(B-2) Polycarbonate Examples of the amorphous thermoplastic resin (b) include polycarbonate (PC). Examples of the polycarbonate used in the present invention include aromatic polycarbonates, aliphatic polycarbonates, and aliphatic-aromatics. Polycarbonate and the like. Among them, aromatic polycarbonates composed of bisphenols such as 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide-based are mentioned. preferable. If necessary, a polycarbonate made of bisphenols substituted with halogen can be used.

The molecular weight of the polycarbonate used is not limited, but is generally 10,000 or more, preferably 20,000 to 40,000.

Examples of other amorphous thermoplastic resins (b) include polystyrene resins, ABS resins, aromatic polysulfones, aromatic polyethersulfones, aromatic amorphous polyamides, silicon resins, polyetherimides, and the like. Poly (alkyl) acrylate and the like can be mentioned, but polyphenylene ether, polycarbonate, and polystyrene resin are preferable, and polyphenylene ether is more preferable.

The amorphous thermoplastic resin (b) used in the present invention may be used in combination of two or more kinds.

<Thermoplastic Resin (c)> The thermoplastic resin (c) used in the present invention is a thermoplastic resin which is non-uniformly mixed with the component (a) and / or the component (b). It is preferably a rubber-like polymer and has a tensile modulus of 5,000 kg / cm.
² (ASTM D882) or less is more preferred.

The rubbery polymer includes, for example, a hydrogenated product of a block copolymer comprising an aromatic vinyl compound polymer block A and a conjugated diene compound polymer block B, and a hydrogenated product of the block copolymer. Is a block B of an aromatic vinyl compound-conjugated diene block copolymer having a structure having at least one chain block A derived from an aromatic vinyl compound and at least one chain block B derived from a conjugated diene. It is a block copolymer that has been reduced by the polymerization. The arrangement of blocks A and B is
It includes those having a linear structure or those having a branched structure (radical teleblock). Further, a part of these structures may include a random chain derived from a random copolymer part of an aromatic vinyl compound and a conjugated diene. Among these, those having a linear structure are preferable,
Those having a diblock structure are more preferred.

The aromatic vinyl compound is preferably styrene, α-methylstyrene, vinyltoluene, vinylxylene, and more preferably styrene.

The conjugated diene is preferably 1,3-
Butadiene and 2-methyl-1,3-butadiene.

The proportion of the repeating unit derived from the aromatic vinyl compound in the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer is preferably in the range of 10 to 80% by weight, and more preferably in the range of 15 to 60% by weight. Is more preferred.

The proportion of unsaturated bonds derived from the conjugated diene and remaining without hydrogenation in the aliphatic chain portions in these block copolymers is preferably 20% or less, more preferably 10% or less. . Further, about 25% or less of the aromatic unsaturated bond derived from the aromatic vinyl compound may be hydrogenated.

These hydrogenated block copolymers have a viscosity of toluene solution at 25 ° C. of 30,000 to 10 cP (concentration: 15% by weight) as a standard of their molecular weight.
And more preferably in the range of 10.0
It is 00-30 cP. If the value is greater than 30,000 cP, the moldability of the final composition becomes difficult,
When the value is smaller than cP, the mechanical strength level of the final composition is undesirably low.

Further, as the rubbery polymer used in the present invention, a polyolefin-based copolymer can be mentioned, preferably an ethylene-propylene copolymer-based rubber and an ethylene-butene copolymer-based rubber. An amorphous random copolymer containing ethylene and propylene and ethylene and butene as main components, in particular, a copolymer of a non-conjugated diene. In this case, as the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylnorbornene, 5-ethylidene-2-norbornene and the like are used.

These ethylene-propylene copolymer rubbers were produced by performing polymerization using a vanadium catalyst comprising a vanadium compound such as vanadium chloride and vanadium oxychloride and an organic aluminum compound such as triethylaluminum sesquichloride. Things are typical. The copolymer rubber produced by such a catalyst system generally has good randomness, shows little crystallinity, and preferably has a crystallinity of less than 20%.

Further, maleic acid, maleic acid monomethyl ester, maleic anhydride,
Α, β-unsaturated dicarboxylic acids such as itaconic acid, itaconic acid monomethyl ester, itaconic anhydride and fumaric acid; endo-bicyclo [2.2.1] -5-heptene-2,3
Alicyclic carboxylic acids such as dicarboxylic acids or derivatives thereof; compounds having a glycidyl group and a (meth) acrylate group in the same molecule; compounds having a glycidyloxy group and an acrylamide group in the same molecule; an alicyclic epoxy group Or an epoxy-containing compound such as butyl glycidyl maleate obtained by graft polymerization using peroxide, ionizing radiation, ultraviolet light, or the like.

The thermoplastic resin (c) used in the present invention comprises:
It is preferable that the component (a) and / or the component (b) be mixed inhomogeneously and that the component (a) and / or the component (b) be compatible. Compatibility here means chemically, for example by a graft or block polymerization reaction, and physically, for example, changing the interfacial properties of the dispersed phase and / or enhancing its dispersion.

<Inorganic Filler (d)> The inorganic filler (d) used in the present invention preferably has an average particle size of 5 μm or less, preferably 4 μm or less, particularly preferably 2.5 μm or less. Here, the average particle size is an average maximum particle size of primary particles measured by observation with an electron microscope. The shape of the inorganic filler is spherical, cubic, granular, needle-like, plate-like,
There are various types such as a fibrous shape, and any of them can be used. Among them, a plate-like shape is preferable from the viewpoint of the balance of physical properties of rigidity and impact resistance and the effect of improving dimensional stability.

As such an inorganic filler (c), a metal element (for example, Fe, N) in Groups I to VIII of the periodic table is used.
a, K, Cu, Mg, Ca, Zn, Ba, Al, Ti)
Or a simple substance of silicon element, oxide, hydroxide, carbon salt, sulfate, silicate, sulfite, various viscosity minerals consisting of these compounds, and others, specifically, for example, titanium oxide, zinc oxide, Barium sulfate, silica, calcium carbonate, iron oxide, alumina, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide,
Magnesium carbonate, calcium sulfate, sodium sulfate,
Calcium sulfite, calcium silicate, kurewalastonite, glass beads, glass powder, silica sand, silica stone, quartz powder, whitebait, diatomaceous earth, white carbon,
Iron powder, aluminum powder and the like can be mentioned, and these may be used in combination of two or more kinds.

Among them, talc, mica, kaolin clay, diatomaceous earth and the like having an average particle size of 5 μm or less are particularly preferable because they are plate-like.

These inorganic fillers (d) may be used without any treatment. However, in order to enhance the affinity with the resin or the interfacial bonding force, an inorganic surface treating agent, that is, a higher fatty acid or an ester or salt thereof is used. Derivatives (e.g., stearic acid, oleic acid, palmitic acid, calcium stearate, magnesium stearate, aluminum stearate, stearamide, ethyl stearate, methyl stearate, calcium oleate, calcium oleate, oleamide, ethyl oleate, Coupling agents (eg, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-A); calcium palmitate, palmitic amide, ethyl palmitate, etc. Minopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.); Titanium coupling agents (eg, isopropyltriisostyaloyl titanate, isopropyltrilauryl myristyl titanate, isopropylisostearoyldiene) Methacryl titanate, isopropyl tridiisooctyl phosphate titanate, etc.) can be used.

The inorganic filler used in the present invention may be glass fiber, preferably having an average diameter of 15 μm or less, and more preferably having an average diameter of 1 to 10 μm, which further enhances the balance of physical properties (heat resistance rigidity, impact strength) and molding. It is preferable in that the warp deformation / reheating warp deformation can be further reduced.

Although the length of the glass fiber is not specified, roving supply, chopped strand of about 1 to 8 mm and the like are preferable. In this case, the number of convergence is usually 1
00 to 5,000 are preferable. If the average length after kneading can be 0.1 mm or more, a so-called milled fiber or a crushed strand of glass powder called glass powder may be used, or a continuous fiber sliver may be used. The composition of the raw glass is preferably non-alkali, and one example is E glass.

If the average diameter of the glass fibers exceeds 15 μm, the degree of improvement in mechanical strength is reduced, and the amount of warpage during molding is undesirably increased. Here, the average diameter is observed with an electron microscope or the like, and the average indicates a number average.

Here, the sizing agent is usually composed of a film forming agent, a surfactant, a softener, an antistatic agent, a lubricant and the like, but may be only a surface treatment agent.

When these glass fibers are used, various coupling agents can be used for the purpose of increasing the affinity with the resin or the interfacial bonding force.

The coupling agent is usually a silane compound,
Includes chrome-based, titanium-based coupling agents and the like. Among them, those containing a silane coupling agent such as epoxy silane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; aminosilane such as γ-aminopropyltriethoxysilane are preferable. At this time, non-ionic, cationic or anionic type surfactants and fatty acids, metal soaps, and various dispersants such as resins can be combined to perform the treatment in terms of improving mechanical strength and kneading properties. preferable.

<Composition Ratios of Constituent Components> The composition ratios of the components (a) to (d) described above are determined by the components (a), (b),
Assuming that the total weight of (c) and (d) is 100% by weight, it is as follows.

The component (a) is 5 to 80% by weight, preferably 7 to 75% by weight, more preferably 10 to 65% by weight. If the component (a) is less than 5% by weight, dimensional stability (linear expansion coefficient) and rigidity are unsatisfactory, and if it exceeds 80% by weight, dimensional stability (linear expansion coefficient) and impact resistance are unsatisfactory.

The component (b) is 5 to 80% by weight, preferably 10 to 70% by weight, more preferably 15 to 50% by weight. If component (b) is less than 5% by weight, the dimensional stability (linear expansion coefficient) and rigidity are unsatisfactory, and if it exceeds 80% by weight, the dimensional stability (linear expansion coefficient) and impact resistance are unsatisfactory.

Component (c) is 10 to 60% by weight, preferably 10 to 55% by weight, more preferably 12 to 4% by weight.
0% by weight. If the component (c) is less than 10% by weight, dimensional stability and impact strength are unsatisfactory, and if it exceeds 60% by weight, dimensional stability and rigidity are insufficient.

Component (d) is 2 to 40% by weight, preferably 5 to 35% by weight, more preferably 8 to 25% by weight. If the component (d) is less than 2% by weight, the dimensional stability is unsatisfactory, and if it exceeds 40% by weight, the impact resistance becomes unsatisfactory.

<Form of Thermoplastic Resin Composition> In the form of the composition of the present invention, the component (c) exists in the form of a network in the component (a) and / or the component (b). By image processing, a component (a) closed in the network existing in a square having a side of 1 μm
And / or measuring the number m of matrix areas of component (b),

[0076]

(Equation 3)

The average value of R is calculated to be an index of 0.9 or less, and the average value of R is preferably 0.85 or less, and more preferably 0.8 or less.
80 or less.

Further, the component (c) is substantially the same as the component (a)
It is essential that it be present at the interface between component (b) and component (c), preferably at least 80% of component (c), more preferably 9%
5% or more is present at the interface between component (a) and component (b). When the component (c) is present in the component (a) and / or the component (b), the dimensional stability becomes unsatisfactory.

It is essential that the component (d) is substantially present in the component (a), and preferably 80% of the component (d)
%, More preferably 95% or more, is present in component (a). When the component (d) is present other than the component (a), the dimensional stability and rigidity are unsatisfactory.

<Melt Shear Viscosity Ratio of Component (a) and Component (c)> The melt shear viscosity ratio of component (a) and component (c) may be any value, but is preferably component (c). The melt shear viscosity ratio of the component (a) is less than 1.0, more preferably 0.9 or less, further preferably 0.85 or less, and particularly preferably 0.8 or less.

The term “melt shear viscosity” used herein means JI.
It is a method described as a reference test of SK7210, that is, a shear viscosity (shear viscosity) when a molten resin is extruded from a capillary at a constant speed, and a specific measurement device is an elevated flow tester. (Instron Capillary Rheometer). Using this apparatus, the measurement can be performed, for example, by setting the cylinder temperature to 280 ° C., the nozzle diameter to 1 mm, and the nozzle length to 10 mm, and changing the extrusion speed. The melt shear viscosity used here was a value at a shear rate of 50 to 300 sec ^-1 .

<Additional Components> Other additional components can be added to the thermoplastic resin composition according to the present invention.
For example, a compatibilizer that makes different thermoplastic resins compatible with each other, and a known antioxidant, weather resistance improver, nucleating agent, flame retardant, impact resistance improver, plasticizer, and fluidity improver for thermoplastic resins. Agents and the like can be used. In some cases, an organic peroxide may be added. The addition of organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., is effective in improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various colorants and their dispersants can be used well-known ones.

<Production and Molding Method of Composition> The production method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, and for example, a melt mixing method or a solution mixing method can be used. As a typical method of melt mixing, use of a melt kneader generally used for thermoplastic resins can be mentioned. For example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, and the like.

As the solution mixing method, there is a method of dissolving each component in an appropriate solvent or mixing them in a suspended state.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, namely, injection molding, hollow molding, extrusion molding, sheet molding, heat molding, and the like. Various molding methods such as molding, rotational molding, lamination molding, and press molding can be applied.

[0086]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following, the parts are important.

Examples 1 to 7 The components used are as follows. Component (a): (a-1) Saturated polyester: polybutylene terephthalate (manufactured by Kanebo, trade name: PBT128) (a-2) Polyamide: polyamide 6 (manufactured by Kanebo, trade name: MC112L, relative to JIS K6810) (Viscosity 2.7) (a-3) Polyolefin: propylene-ethylene block copolymer (manufactured by Mitsubishi Yuka Co., trade name: BC8DQ, J
MFR according to IS K7210: 1.2 g / 10 min, ethylene content by infrared spectroscopy: 5.5% by weight)

Component (b): (b-1) Polyphenylene ether: poly (2,6-dimethyl-1,4-phenylene ether) (produced by Nippon Polyether Co., Ltd., intrinsic viscosity measured at 30 ° C. in chloroform: 0.30 dl / g) (b-2) Modified polyphenylene ether: 100 parts of polyphenylene ether (b-1), 2 parts of commercially available maleic anhydride, and 4 parts of polyamide 6 (a-2) are sufficiently mixed and stirred with a super mixer. The mixture was melt-kneaded using a twin-screw extruder (TEX44, manufactured by Nippon Steel Works Co., Ltd.) under kneading conditions of a set temperature of 250 ° C. and a screw rotation speed of 200 rpm to form a resin composition, which was then pelletized and dried under reduced pressure. Thus, a modified polyphenylene ether was obtained. (B-3) Polycarbonate: polycarbonate (Mitsubishi Gas Chemical Company, trade name: Iupilon (E-2000)) (b-4) Polyolefin: propylene-ethylene block copolymer (same as component (a-3))

Component (c): (c-1) SEBS: hydrogenated aromatic vinyl-conjugated diene block copolymer (Creton G1652 manufactured by Shell Chemical Co., Ltd.) (c-2) Modified SEBS1: aromatic vinyl- 100 parts of a hydrogenated product of a conjugated diene block copolymer (c-1), 5 parts of an epoxidized acrylamide compound (manufactured by Kaneka Chemical Industry Co., Ltd., trade name: Kaneka AXE) as an unsaturated polar compound,
1,3-bis (t-butylperoxyisopropyl) benzene (Percadox 14 manufactured by Kayaku Nuuri Co., Ltd.)
And 1 part thereof were sufficiently mixed and stirred by a super mixer, and the mixture was set at a set temperature of 180 ° using a twin screw extruder (TEX44).
The mixture was melted and kneaded under kneading conditions at 200 ° C. and a screw rotation speed of 200 rpm to obtain a resin composition and then pelletized. The pellet was washed with acetone and dried under reduced pressure to obtain a modified resin. According to the infrared absorption spectrum measurement of this modified resin, the amount of the unsaturated polar compound graft-polymerized was 1.6% by weight.
Met. (C-3) Modified SEBS2: hydrogenated maleic anhydride-modified aromatic vinyl-conjugated diene block copolymer (Creton G1901X manufactured by Shell Chemical Company)

Component (d): (d-1) Talc: KT-300, manufactured by Fuji Talc, average particle size: 1.5 μm (d-2) Potassium titanate: Tismo D102, manufactured by Otsuka Chemical Co., Ltd. 3) Clay: KT-17, manufactured by Kinsei Matech
0, average particle size: 0.6 μm

Other components: PEP36: bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: MarkPEP-36, manufactured by Asahi Denka Co., Ltd .; hereinafter referred to as “PEP3”)
6)) Maleic anhydride: Commercially available maleic anhydride (reagent grade) Epoxy compound: Epoxidized acrylamide compound (Kaneka AXE, manufactured by Kaneka Chemical Industry Co., Ltd.)

The components (a) and (d) are
At a compounding ratio shown in Table 1, a twin-screw extruder (TEX44 manufactured by Nippon Steel Works) was melt-kneaded at a set temperature of 230 ° C. and a screw rotation speed of 250 rpm, and pelletized. Next, the pellets and the remaining components (b) and (c) were sufficiently mixed and stirred with a supermixer at the compounding ratio shown in Table 1, and the mixture was set at a set temperature using the twin-screw extruder. The mixture was melt-kneaded at 230 ° C., a screw rotation number of 350 rpm, and vented at 600 mmHg to form a resin composition and then pelletized.

From the pellets of the above resin composition, an in-line screw type injection molding machine (IS, manufactured by Toshiba Machine Works, Ltd.)
(-90B type), injection molding was performed at a cylinder temperature of 280 ° C. and a mold cooling temperature of 80 ° C. to prepare test pieces.

In the injection molding, drying was performed for 48 hours under the conditions of 0.1 mmHg and 80 ° C. using a reduced pressure dryer immediately before the injection molding. The injection-molded test piece was placed in a desiccator immediately after molding and allowed to stand at 23 ° C. for 4 to 6 days. After that, an evaluation test was performed according to the following method, and the results are shown in Table 1.

(1) Dispersion Form (R Calculation Method) A sample was cut out from an injection-molded article or a pellet obtained by kneading, and RuO ₄ and OsO _{4 were} stained. Ultra-thin sections are prepared using the cut N) and observed with a transmission electron microscope (JEM100CX manufactured by JEOL Ltd.). The component (b) is observed to be black by staining, and its existing state can be observed. Further, the observed photograph was binarized by an image processing analyzer (Spica 2 manufactured by Nippon Avionics Co., Ltd.) and closed by a network of component (c) existing in a square of 1 μm on a side. The number m of the existing matrix areas is calculated, and R is calculated by equation (I). This analysis was performed on a representative place of the molded article or the pellet, and the average value was obtained and used as an index of the network structure. Further, the locations of the components (c) and (d) can be observed by the above method.

(2) Melt shear viscosity ratio (component (c) / component (a) and component (c) / component (b)) Instron capillary according to the method described as a reference test of JIS K7210 -The melt shear viscosity of each component was measured using a rheometer.

(3) Three-point flexural modulus ISO R178-1974 Procedure 12 (JIS
K 7203) using an Instron tester.

(4) Izod impact strength ISO R180-1969 (JIS K 7110)
It was measured using an Izod impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to the notched Izod impact strength.

(5) Linear expansion coefficient The linear expansion coefficient was measured according to ASTM D696. However, the measurement temperature range is 23 to 80 ° C.

(6) Heat deformation temperature Using an HDT tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.),
The evaluation was performed at a load of 4.6 kg according to SK 7207.

[0101]

[Table 1]

[0102]

[Table 2]

For the composition obtained in Example 1, 7
FIG. 1 shows a transmission electron micrograph at a magnification of 5,000.
The staining shows that component (c) (here, modified SEBS) forms a fibrous network structure. The number m of regions of the polybutylene terephthalate closed with the modified SEBS is 12, and the R value is 0.56.

Comparative Example 1 The same procedure as in Examples 1 to 7 was carried out using the composition shown in Table 1 except that the following modified SEBS (c-4) was used as the component (c). Table 1 shows the results.

(C-4): Modified SEBS: 100 parts of a hydrogenated aromatic vinyl-conjugated diene block copolymer (Claton G1651 manufactured by Shell Chemical Co., Ltd.), 2 parts of maleic anhydride and 1 part of unsaturated polar compound , 3-bis (t
-Butyl peroxyisopropyl) benzene (Perkadox 14 manufactured by Kayaku Nuuri Co., Ltd.) was sufficiently mixed and stirred with a super mixer, and the mixture was mixed with a twin-screw extruder (T
Using EX44), the mixture was melt-kneaded at a set temperature of 180 ° C. and a screw rotation speed of 200 rpm to obtain a resin composition, which was then pelletized. After washing the pellet with acetone,
Drying under reduced pressure gave a modified resin. According to the infrared absorption spectrum of this modified resin, the amount of graft polymerization of the unsaturated polar compound was 0.8% by weight.

Comparative Example 2 The same procedure as in Examples 1 to 7 was carried out except that the components (a) to (d) were simultaneously mixed and stirred at a mixing ratio shown in Table 1 using a super mixer. Table 1 shows the results.

For the composition obtained in Comparative Example 2, 7
FIG. 2 shows a transmission electron micrograph at a magnification of 5,000.
Component (d) is observed as white, and component (b) and component (c)
You can see that it exists inside.

[0108]

According to the results of the above evaluation test, component (c) has a network form in component (a) and / or component (b), and component (c) is substantially equivalent to component (a). The thermoplastic resin composition of the present invention, which is present at the interface of the component (b) and the component (d) is substantially present in the component (a), has dimensional stability (low coefficient of linear expansion), rigidity and resistance. It can be seen that the impact balance is excellent. Therefore, its use is wide and it can be an industrially useful material.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph (magnification: 75,000) showing a fibrous particle structure of a composition obtained in Example 1.

FIG. 2 is a transmission electron micrograph (75,000 times) showing a fibrous particle structure of the composition obtained in Comparative Example 2.

Continuation of front page (56) References JP-A-63-92668 (JP, A) JP-A-63-128076 (JP, A) JP-A-53-124559 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (1)

(57) [Claims] 1. A crystalline thermoplastic resin component (a), an amorphous thermoplastic resin component (b) mixed heterogeneously with component (a), and a rubber mixed heterogeneously with component (a) and component (b). A resin composition comprising the polymer (c) and the inorganic filler (d), wherein the total amount of the components (a), (b), (c) and (d) is 100% by weight, and the component (a) ) 5-8
0% by weight, component (b) 5 to 80% by weight, component (c) 10
-60% by weight and 2-40% by weight of component (d), wherein component (c) forms a network form, and at least 80% of component (c) is at the interface between component (a) and component (b). The number of regions of the components (a) and / or (b) that are present and are closed by the network of the component (c) existing in a square of 1 μm on a side is represented by m, and the formula (I): The average value of the index R represented by is 0.9 or less, and the component (c) according to the method described in JIS K 7210
Wherein the ratio of the melt shear viscosity of the component (a) to the component (a) is less than 1.0, and at least 80% of the component (d) is present in the component (a). object.